JP3248184B2 - Method for producing 1,1,1,3,3-pentafluoropropane and method for producing 1,1,1,3,3-pentafluoro-2,3-dichloropropane - Google Patents

Abstract

A method of producing 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane characteriized by fluorinating a halogenated propene indicated by the general formula I: <CHEM> (provided that in the general formula, X and Y are respectively Cl or F) with hydrogen fluoride in the presence of antimony trihalogenide and/or antimony pentahalogenide in a liquid phase, wherein the hydrogen fluoride is present in the reaction system in a mole ratio of or over five times that of antimony trihalogenide and/or antimony pentahalogenide. This process can provide the desired product at low cost in high yields on an industrial scale.

Description

The present invention is a useful compound that can be used as a substitute for CFC and HCFC used as a refrigerant, a blowing agent, and a cleaning agent. In particular, a method for producing 1,1,1,3,3-pentafluoropropane useful as a urethane foaming agent, and a 1,1,1,3,3-pentafluoro-2,3 The present invention relates to a method for producing dichloropropane.

2. Description of the Related Art As a method for producing 1,1,1,3,3-pentafluoropropane, a hydrogen reduction reaction (USP 2,942,036) using 1,2,2-trichloropentafluoropropane as a raw material is known.

However, according to this method, 2-chloropentafluoropropene having a low yield and not sufficiently reduced,
Since it produces 1,3,3,3-pentafluoropropene, it is not industrially suitable.

On the other hand, 1,1,1,3,3-pentafluoro-2-halogeno-
3-chloropropane itself is useful as an intermediate for medical and agricultural chemicals, and is used as a refrigerant, a blowing agent, and a cleaning agent by performing fluorination or reduction.
It is an industrially useful compound that can be derived from hydrofluorocarbons as substitutes for C and CFC, and can be derived into monomers of various resins by dehydrochlorination. In particular, 1,1,1,3,3-pentafluoro-2,3-dichloropropane can be useful as a raw material for 1,1,1,3,3-pentafluoropropane.

Heretofore, a method of fluorinating a halogenated propene in a liquid phase with HF in the presence of an antimony halide has been known. For example, ETMcBee et al. Disclose 1,1,1-trifluoro-
2,3,3-Trichloropropene is fluorinated with HF in the presence of an antimony catalyst to give 1,1,1,3,3-pentafluoro-2,3-dichloropropane (J. Am .Chem.So
c. 70 , 2023, (1948)).

However, in this reaction, since the raw materials 1,1,1-trifluoro-2,3,3-trichloropropene, HF, and antimony catalyst are charged at once into the reactor before the reaction, the temperature is as high as 250 ° C. Not only is the reaction temperature necessary,
The yield of 1,1,1,3,3-pentafluoro-2,3-dichloropropane is as low as 50%, which cannot be said to be an industrially feasible reaction.

In addition, 1,1,1,2,3,3-hexachloropropene is useful as an intermediate for various medical and agricultural chemicals, and the intermediate of various fluorine compounds is synthesized by fluorinating the chlorine of this propene with HF. It is a useful raw material that can be used. In particular, 1,1,1,3,3
-Pentafluoro-2,3-dichloropropane (HCFC225d
Useful as a) raw material.

Generally, 1,1,1,2,3,3-hexachloropropene is
It is synthesized by dehydrochlorination of 1,1,2,2,3,3-heptachloropropane. 1,1,1,2,2,3,3-heptachloropropane as a raw material is an inexpensive industrial material that can be easily synthesized from inexpensive industrial materials, chloroform and tetrachloroethylene.

So far, 1,1,1,2,3,3-hexachloropropene has been
A method is known in which 1,1,1,2,2,3,3-heptachloropropane is dehydrochlorinated with an alkali metal hydroxide such as KOH using an alcohol as a solvent to synthesize (J. Am. Chem. So
c., 63, 1438 (1941)).

However, in this method, since an alcohol is used as a reaction solvent, it is necessary to filter an alkali metal chloride generated after the reaction, and then separate the product from the alcohol by an operation such as distillation.

It is also known that 1,1,1,2,2,3,3-heptachloropropane can be obtained by passing through a reaction tube heated to about 400 ° C., but this reaction requires a high temperature. In addition, it is necessary to use an expensive metal for the material of the reaction tube in order to generate HCl by the reaction.

A first object of the present invention is to provide a method capable of sufficiently producing 1,1,1,3,3-pentafluoropropane (HFC245fa) with high selectivity without causing the above-mentioned problems. Is to do.

A second object of the present invention is to solve the above-mentioned problem which the conventional method for producing 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane has, and to reduce the cost. An object of the present invention is to provide an industrial production method capable of easily producing 1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane (in particular, HCFC225da) with high yield.

Structure of the Invention The present inventor has attempted to solve the above-described problems by using 1,1,1,3,3-
As a result of intensive studies on the production method of pentafluoropropane, hydrogen reduction was carried out using 1,1,1,3,3-pentafluoro-2,3-dichloropropane as a raw material by a gas phase method in the presence of a noble metal catalyst such as palladium. When the reaction (catalytic reduction) was performed, it was found that the desired product could be obtained in high yield, and the first invention was completed.

That is, the gist of the first invention is that 1,1,1,3,3-pentafluoro-2,3-dichloropropane is used as a raw material and the temperature is particularly increased to 30 to 450 ° C. in the presence of a noble metal catalyst such as palladium. In this method, 1,1,1,3,3-pentafluoropropane is produced at a high selectivity of 80% or more by performing a hydrogen reduction reaction by a gas phase method.

In the first invention, it is particularly important to perform hydrogen reduction by a gas phase method using a noble metal catalyst. As a method of the gas phase reaction, a method such as a fixed bed type gas phase reaction and a fluidized bed type gas phase reaction can be employed.

Examples of the noble metal of the noble metal catalyst include palladium and platinum, and palladium is preferable in terms of the selectivity of the reaction, that is, the amount of by-products generated is small, and is selected from activated carbon, silica gel, titanium oxide, zirconia and others. Further, those supported on at least one kind of carrier are preferable.

Further, the particle size of the carrier has little effect on the reaction, but is preferably 0.1 to 100 mm.

Further, the carrier concentration can be widely used as 0.05 to 10 (weight)%, but usually, a 0.5 to 5% carrying product is recommended.

The reaction temperature is usually 30 to 450 ° C., preferably 70 to 450 ° C.
~ 400 ° C.

In the hydrogen reduction reaction of 1,1,1,3,3-pentafluoro-2,3-dichloropropane, the ratio between hydrogen and the raw material can be largely varied. However, hydrogenation is usually carried out using at least a stoichiometric amount of hydrogen. Substantially higher than stoichiometric amounts, for example 8 moles or more, of hydrogen can be used, based on the total moles of starting material.

The pressure of the reaction is not particularly limited, and it is possible under pressure, under reduced pressure, and normal pressure.
It is preferable to carry out the reaction under pressure and normal pressure.

The contact time is usually 0.1-300 seconds, especially 1-30
Seconds.

The raw material 1,1,1,3,3-pentafluoro-2,3-dichloropropane is a known compound, and is a fluorinated 1,1,1-trifluoro-2,3,3-trichloropropene. (ETMcBEE, ANTHONY TRUCHAN an
d ROBOLT, J. Amer. Chem. Soc., vol 70, 2023-2024 (194
8)).

In addition, the present inventor has attempted to solve the above-described problems by using 1,1,1,1,
As a result of intensive studies on the method for producing 3,3-pentafluoropropane, it was found that 1,1,1,3,3-pentafluoro-2,3-dichloropropane was used as a raw material and at least one element selected from zirconium and vanadium. It was found that if the hydrogen reduction reaction was carried out by a gas phase method in the presence of a catalyst in which was added to palladium, the desired product could be obtained in high yield.
Completed the invention.

That is, the gist of the second invention is a catalyst obtained by adding at least one element selected from zirconium and vanadium to palladium using 1,1,1,3,3-pentafluoro-2,3-dichloropropane as a raw material. Especially in the presence of 30-450
There is a method for producing 1,1,1,3,3-pentafluoropropane in a high yield of 80% or more by performing a hydrogen reduction reaction by a gas phase method at a temperature of ° C.

In the second invention, it is particularly important to carry out a hydrogen reduction reaction by a gas phase method using a catalyst in which at least one element selected from zirconium and vanadium is added to palladium. As a method of the gas phase reaction, a method such as a fixed bed type gas phase reaction and a fluidized bed type gas phase reaction can be employed.

The amount of zirconium and / or vanadium to be added to palladium is usually 0.01 to 4 and preferably 0.1 to 2 in molar ratio.

The catalyst to which at least one element selected from zirconium and vanadium is added is preferably a catalyst supported on a carrier made of at least one selected from activated carbon, silica gel, titanium oxide, zirconia and others.

In this case, the metal to be supported may be in the form of a salt, and nitrates, oxide salts, oxides, chlorides and the like can be used for this.

Further, the particle size of the carrier has little effect on the reaction, but is preferably 0.1 to 100 mm.

As the loading concentration, a wide range of 0.05 to 10% can be used, but a loading of 0.5 to 5% is usually recommended.

The reaction temperature is usually 30 to 450 ° C, preferably 70 to 400 ° C.

In the hydrogen reduction reaction of 1,1,1,3,3-pentafluoro-2,3-dichloropropane, the ratio between hydrogen and the raw material can be largely varied. However, hydrogenation is usually carried out using at least a stoichiometric amount of hydrogen. Substantially higher than stoichiometric amounts, for example 8 moles or more, of hydrogen can be used, based on the total moles of starting material.

The pressure of the reaction is not particularly limited, and it is possible under pressure, under reduced pressure, and normal pressure.
It is preferable to carry out the reaction under pressure and normal pressure.

The contact time is usually from 0.1 to 300 seconds, especially from 1 to 30 seconds.

Further, the present inventor has set forth a formula (I): Halogenated propene represented by (for example, 1,1,1,2,3,3-
Hexachloropropene) is fluorinated in the liquid phase with hydrogen fluoride in the presence of antimony trihalide and / or antimony pentahalide, wherein at least 5 times the molar amount of antimony trihalide and / or antimony pentahalide. 1,1,1,3,3 as a starting material of the first and second inventions, characterized in that hydrogen fluoride is present in the reaction system.
-A method for producing pentafluoro-2,3-dichloropropane was found, and the third invention was reached.

The third invention is, for example, fluorinating a halogenated propene of the above general formula I in the coexistence of antimony trihalide, antimony fluoride and HF to give 1,1,1,3,3-pentafluoro- It is for producing 2,3-dichloropropane.

In the third invention, antimony chloride added to the reaction system is partially fluorinated in the presence of HF to form SbClxFy
(X + y = 5), but when used as a catalyst for the fluorination of hydrogen or a compound having a double bond that can be chlorinated, such as halogenated propene,
It has been found that the higher the fluorine content, the faster the fluorination reaction proceeds and the more the chlorination product, which is a by-product, can be suppressed.

Further, by allowing an excess amount of HF to coexist with the added antimony trihalide and / or antimony pentahalide, the fluorine content of the antimony trihalide and / or antimony pentahalide is kept high, and the addition reaction is suppressed. 1,1,1,3,3-pentafluoro-2,3 with good selectivity
-It has been found that dichloropropane can be synthesized, and the third invention has been completed.

The amount of HF charged into the reactor is the sum of the consumed HF and the amount that escapes with the product. That is, this keeps the amount of HF in the reaction system constant. However, fluctuations in the capacity of the reactor are allowed as long as the excess ratio of HF can be maintained. Before the reaction, all the necessary amount of HF can be charged into the reactor.

The amount of halogenated propene introduced into the reactor per hour (the rate of charging) must be reduced with respect to the amount of antimony chloride added to the system. It is not preferable because the production amount per unit decreases.

However, if the amount is too large, the fluorine content of antimony chloride will decrease, and the reaction proceeds, but the selectivity decreases. That is, the introduction amount of the halogenated propene is usually 100
Set to not more than twice mol / Hr and not less than twice mol / Hr. Preferably, the molar ratio is set to 50 times mol / Hr or less and 5 times mol / Hr or more.

If the reaction temperature is 40 ° C. or higher, the reaction proceeds. In this case, the selectivity decreases unless the amount of halogenated propene introduced into the charged antimony chloride is reduced.

High reaction temperatures are also advantageous in terms of productivity and selectivity, but the reaction pressure must be kept high according to the reaction temperature. Maintaining a high reaction pressure increases equipment costs, so in practice the reaction should be at 50 ° C.
It is desirable to carry out in the range of from 150 to 150 ° C.

The reaction pressure is raised according to the reaction temperature, to effect separation of HF with the product, choose a suitable pressure in the range of 3 Kg / cm ² of 30 Kg / cm ^2. Then, while keeping the reaction at a constant pressure, the halogenated propene as a raw material is slowly charged into the reaction system, and hydrogen fluoride is also charged to generate 1,1,
By extracting 1,3,3-pentafluoro-2,3-dichloropropane, the desired product can be obtained in high yield.

Increasing the amount of HF coexisting with antimony chloride in the reaction system does not affect the selectivity of the reaction, but increasing it decreases the productivity per reactor volume. When the amount is small, the reaction proceeds, but the introduced amount of the halogenated propene must be reduced in order to avoid a decrease in selectivity. Practically, the reaction should be carried out with hydrogen fluoride in a molar amount of 5 times or more with respect to antimony chloride, and it is preferable to carry out the reaction in a molar amount of 500 times or less.
More preferably, HF of 50 times or more and 200 times or less is coexisted.

In addition, the antimony trihalide and the antimony trihalide usable in the third invention include, in addition to the above, a mixture of SbF ₃ and SbCl ₅ or a part of SbF ₃ by Cl ₂ to form SbF ₃
Cl ₂ F ₃ can be used.

Further, the present inventor has conducted intensive studies to solve the above-described problems, and as a result, in the dehydrochlorination reaction of heptachloropropane, 1,1,1,2,2,3,3-heptachloropropane and an alkali metal such as an aqueous solution of KOH were used. By reacting the hydroxide with an aqueous solution in the presence of a suitable phase transfer catalyst, it was found that the reaction proceeds under mild reaction conditions.

That is, 1,1,1,2,2,3,3-heptachloropropane is reacted with an aqueous solution of an alkali metal hydroxide in the presence of a phase transfer catalyst, 1,1,1,2, This is a method for producing 3,3-hexachloropropene.

Generally, ionic compounds such as alkali metal hydroxides do not dissolve in heptachloropropane. Therefore, the reaction is generally performed using a compatible solvent such as alcohol. However, in this method, after the reaction, the used reaction solvent must be separated from the produced target. It is also conceivable to carry out the reaction in a two-phase system using an aqueous solution of an alkali metal hydroxide. However, when the reaction is carried out in a two-phase system, the reaction is generally slow and intense conditions are often required.

However, when the reaction in the two-phase system is performed using the aqueous solution of the alkali metal hydroxide in the presence of a phase transfer catalyst, particularly a tetraalkylammonium salt or a tetraalkylphosphonium salt as described below, the reaction becomes mild. It was found that the reaction proceeded promptly under the appropriate conditions.

Examples of the cation of the tetraalkylammonium salt used in the reaction include benzyltriethylammonium, trioctylmethylammonium, tricaprylmethylammonium, and tetrabutylammonium.

Examples of the cation of the tetraalkylphosphonium salt include tetrabutylphosphonium and trioctylethylphosphonium.

The cation and the anion constituting the salt are not limited, but generally include a chloride ion and a hydrogen sulfate ion.

However, the above is merely an example, and does not limit the type of catalyst.

Examples of the alkali metal hydroxide that can be used in the above reaction include NaOH and KOH. The concentration of the aqueous solution of the alkali metal hydroxide is not limited.
%, Desirably at 20-40%.

These aqueous solutions can be reused after the reaction by removing the generated alkali metal chloride by a precipitation method, filtration, or the like, and again adding an alkali metal hydroxide.

The reaction is carried out in a two-phase system, and the phases are easily separated to obtain a target 1,1,1,2,3,3-hexachloropropene crude product. The resulting crude product can be easily purified by distillation,
It is possible to recover the used catalyst and unreacted heptachloropropane.

The reaction temperature is usually from room temperature to 80 ° C., preferably 40 ° C.
Perform at ~ 60 ° C.

Further, 1,1,1,2,2,3,3-heptachloropropane, which is a raw material, can be obtained by reacting tetrachloroethylene with chloroform in the presence of a Lewis acid catalyst such as aluminum chloride (Japanese Patent Application Laid-Open (JP-A) No) No. 61-118333).

Regarding the first to third inventions described above, the products obtained by the production methods of the respective inventions can be used as follows.

First, 1,1,1,2,3,3 obtained by the above manufacturing method
-Hexachloropropene as a raw material, which is prepared according to the production method of the third invention to form 1,1,1,3,3-pentafluoro-2,3-
To dichloropropane, which is used in the first invention or the second invention.
Can lead to 1,1,1,3,3-pentafluoropropane. By this series of steps, the desired product can be obtained in high yield from inexpensive raw materials available in the container, and it is economically excellent.

In this case, 1,1,1,2,3,3-hexachloropropene obtained above is converted to 1,1,1,3,3 by the production method of the third invention.
Lead to pentafluoro-2,3-dichloropropane, which can be taken off as product. In this step, there is an advantage that the obtained product can be used as an intermediate for medical and agricultural chemicals or an intermediate for resin monomer.

Further, 1,1,1,1 obtained by the manufacturing method of the third invention.
3,3-pentafluoro-2,3-dichloropropane is used as a raw material, which can be led to 1,1,1,3,3-pentafluoropropane by the production method of the first or second invention. . This series of steps has the advantage that 1,1,1,3,3-pentafluoropropane, which is important as a urethane blowing agent, can be obtained in high yield.

INDUSTRIAL APPLICABILITY The first and second inventions use 1,1,1,3,3-pentafluoro-2,3-dichloropropane as a raw material, particularly in the presence of a noble metal catalyst such as a palladium catalyst. Since the hydrogen reduction reaction is performed at a temperature of about 450 ° C., 1,1,1,3,3-pentafluoropropane can be produced with a high selectivity of 80% or more.

In a third aspect of the present invention, a halogenated propene of the general formula I is mixed with hydrogen fluoride in a liquid phase in the presence of antimony trihalide and / or antimony pentahalide in an amount of at least 5 times mol of the antimony halide in a liquid phase. Therefore, it is possible to provide an industrial production method capable of producing 1,1,1,3,3-pentafluoro-2,3-dichloropropane at low cost, easily and with high yield.

Examples Hereinafter, various examples of the present invention will be described, but these examples can be variously modified based on the technical idea of the present invention.

Example 1 In a SUS316 reaction tube having an inner diameter of 2 cm and a length of 40 cm, 0.5 g of activated carbon was added.
The mixture was filled with 20 cc of a palladium catalyst supported at a concentration of 0.2%, and heated to 250 ° C. in an electric furnace while flowing nitrogen gas. After reaching a predetermined temperature, the nitrogen gas was changed to hydrogen gas and flowed for a while.

Next, 1,1,1,3,3-pentafluoro-2,3-dichloropropane, which had been vaporized in advance, was introduced into the reaction tube at 16.7 cc / min and hydrogen gas was introduced at 140 cc / min. The reaction temperature was kept at 250 ° C.

The generated gas was washed with water, dried over calcium chloride, and analyzed by gas chromatography. The results are shown in Table 1.

Example 2 The flow rate of hydrogen gas was 140 cc / min, 1,1,1,3,3-pentafluoro-2,3-dichloropropane was 17 cc / min, and the reaction temperature was 27 cc / min.
The reaction was carried out in the same manner as in Example 1 except that the temperature was raised to 0 ° C. The results are shown in Table 1.

From these results, the target compound can be obtained with a high selectivity of 80% or more at a conversion of 100% by the reaction according to the first invention.

Example 3 A reaction tube made of SUS316 having an inner diameter of 2 cm and a length of 40 cm was filled with 20 cc of a catalyst having activated carbon loaded with 0.5% of palladium and 0.25% of zirconium.
Heated to 0 ° C. After reaching a predetermined temperature, the nitrogen gas was changed to hydrogen gas and flowed for a while.

Next, 1,1,1,3,3-pentafluoro-2,3-dichloropropane, which had been vaporized in advance, was introduced into the reaction tube at 16.7 cc / min and hydrogen gas was introduced at 140 cc / min. The reaction temperature was kept at 250 ° C.

The generated gas was washed with water, dried over calcium chloride, and analyzed by gas chromatography. The results are shown in Table 2.

Example 4 A reaction was carried out in the same manner as in Example 3, except that the flow rate of hydrogen gas was changed to 120 cc / min and 1,1,1,3,3-pentafluoro-2,3-dichloropropane was changed to 35 cc / min. Was. The results are shown in Table 2.

Example 5 Catalyst 2 in which 0.5% of palladium and 0.25% of vanadium were supported on activated carbon in a SUS316 reaction tube having an inner diameter of 2 cm and a length of 40 cm
0 cc, 250 ° C in an electric furnace while flowing nitrogen gas
Heated. After reaching a predetermined temperature, the nitrogen gas was changed to hydrogen gas and flowed for a while.

Next, 1,1,1,3,3-pentafluoro-2,3-dichloropropane, which had been vaporized in advance, was introduced into the reaction tube at 16.7 cc / min and hydrogen gas was introduced at 140 cc / min. The reaction temperature was kept at 250 ° C.

The generated gas was washed with water, dried over calcium chloride, and analyzed by gas chromatography. The results are shown in Table 2.

Example 6 A reaction was carried out in the same manner as in Example 5, except that the flow rate of hydrogen gas was changed to 280 cc / min and 1,1,1,3,3-pentafluoro-2,3-dichloropropane was changed to 32 cc / min. Was. The results are shown in Table 2.

From this result, the target compound can be obtained with a high selectivity of 80% or more at a conversion of 100% by the reaction according to the second invention.

The SbCl ₅ to 500ml Hastelloy autoclave with Example 7 condenser was placed 29.9 g (0.1 mol), after cooling it was added HF300g (15mol). Thereafter, the temperature was gradually increased, and the reaction was carried out at 80 ° C. for 3 hours.

While maintaining the temperature at 80 ° C., 1,1,1,2,3,3-hexachloropropene was added at 0.2 mol / Hr and HF at 1.2 mol / Hr. As the weight of the reactor becomes constant, the reaction pressure from 9Kg / cm ² 1
It was controlled within the range of 1 kg / cm ² .

During the reaction, the generated hydrochloric acid and the product were extracted from the upper part of the condenser, and the product was collected with a dry ice trap after washing the hydrochloric acid with water. When 249 g (1 mol) of 1,1,1,2,3,3-hexachloropropene was added, the reaction was stopped.

After the reaction, the pressure was gradually reduced, and the contents were extracted. 190 g of organic material were obtained as the product.

97% of the product is the target 1,1,1,3,3-pentafluoro-2,3-dichloropropane which can be used as a starting material in Example 1 and the like (hereinafter the same). GLC confirmed (91% yield). The main by-product is the reaction intermediate 1,
It was 1,1,3-tetrafluoro-2,3,3-trichloropropane, and no halogenated propane to which chlorine was added was observed.

Reference Example 1 placed SbCl ₅ to 500ml Hastelloy autoclave equipped with a condenser 29.9 g (0.1 mol), after which it was cooled, added HF300g (15mol). Thereafter, the temperature was gradually increased, and the reaction was carried out at 80 ° C. for 3 hours.

While maintaining the temperature at 80 ° C, 1,1,1,2-tetrafluoro-3,3-dichloropropene is 0.2 mol / Hr and HF is 0.6 mol / Hr.
Added in. The reaction pressure was controlled in the range from 9 kg / cm ² to 11 kg / cm ² .

During the reaction, the generated hydrochloric acid and the product were extracted from the upper part of the condenser, and the product was collected with a dry ice trap after washing the hydrochloric acid with water. 1,1,1,2-tetrafluoro-3,3-
The reaction was stopped when 183 g (1 mol) of dichloropropene was added.

After the reaction, the pressure was gradually reduced, and the contents were extracted. 177 g of organic matter was obtained as a product.

GLC confirmed that 98.5% of the product was the desired 1,1,1,2,3,3-hexafluoro-3-chloropropane (94% yield).

The main by-product was 1,1,1,2,3-pentafluoro-3,3-dichloropropane, a reaction intermediate, and no halogenated propane to which chlorine had been added was observed.

The SbCl ₅ to 500ml Hastelloy autoclave with Example 8 condenser was placed 29.9 g (0.1 mol), after cooling it was added HF300g (15mol). Thereafter, the temperature was gradually increased, and the reaction was carried out at 80 ° C. for 3 hours.

While maintaining the temperature at 80 ° C., 1,1,1-trifluoro-2,
0.2 mol / Hr for 3,3-trichloropropene, 0.8 mol / Hr for HF
Added in. The reaction pressure was controlled in the range from 10 Kg / cm ² of 12 Kg / cm ^2.

During the reaction, the generated hydrochloric acid and the product were extracted from the upper part of the condenser, and the product was collected with a dry ice trap after washing the hydrochloric acid with water. The reaction was stopped when 199 g (1 mol) of 1,1,1-trifluoro-2,3,3-trichloropropene was added.

After the reaction, the pressure was gradually reduced, and the contents were extracted. 198 g of organic matter was obtained as a product.

GLC confirmed that 98% of the product was the desired 1,1,1,3,3-pentafluoro-2,3-dichloropropane (96% yield).

The main by-product was 1,1,1,3-tetrafluoro-2,3,3-trichloropropane, a reaction intermediate, and no halogenated propane to which chlorine was added was observed.

Example 9 29.9 g (0.1 mol) of SbCl ₅ and 17.9 g (0.1 mol) of SbF ₃ were added to a 500 ml Hastelloy autoclave equipped with a condenser.
The reaction was carried out in the same manner as in Example 7, except that it was added.

196 g of organic matter was obtained as a product. GLC confirmed that 98% of the product was the desired 1,1,1,3,3-pentafluoro-2,3-dichloropropane (94% yield). The main by-product was 1,1,1-tetrafluoro-2,3,3-trichloropropane, and no compound to which chlorine was added was observed.

From the above results, by the reaction based on the third invention,
1,1,1,3,3-pentafluoro-2-halogeno-3-chloropropane can be produced easily and in high yield.

Example 10 1,1,1,2,2,3,3-heptachloropropane 2 was placed in a 500 ml round bottom flask equipped with a Dimroth condenser and a dropping funnel.
85.5 g (1.0 mol) and 0.3 g (0.1 mmol) of tetrabutylammonium chloride were charged.

While maintaining the temperature at 40 ° C. and stirring vigorously, 250 ml of a 20% aqueous KOH solution was added dropwise over 1 hour. After the addition, the stirring was stopped and the lower organic layer was analyzed. 1,1,1, the raw material
2,2,3,3-heptachloropropane disappears and the organic layer is 1,
There was only 1,1,2,3,3-hexachloropropene.

The reaction solution was transferred to a separating funnel, and the organic layer was separated. After washing twice with saturated saline, drying over magnesium sulfate, 23
7 g (95%) of crude 1,1,1,2,3,3-hexachloropropene (which can be used as a starting material for Example 7 and the like; hereinafter the same) were obtained.

Example 11 1,1,1,2,2,3,3-heptachloropropane 2 was placed in a 500 ml round bottom flask equipped with a Dimroth condenser and a dropping funnel.
85.5 g (1.0 mol) and 0.3 g (0.1 mmol) of tricaprylmethylammonium chloride were charged.

While maintaining the temperature at 40 ° C. and stirring vigorously, 250 ml of a 20% aqueous KOH solution was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was carried out for one hour. Thereafter, the stirring was stopped and the lower organic layer was analyzed. The raw material 1,1,1,2,2,3,3-heptachloropropane disappeared, and the organic layer was only 1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred to a separating funnel, and the organic layer was separated. After washing twice with saturated saline, drying over magnesium sulfate, 23
2 g (93%) of crude 1,1,1,2,3,3-hexachloropropene were obtained.

Example 12 1,1,1,2,2,3,3-heptachloropropane 2 was placed in a 500 ml round bottom flask equipped with a Dimroth condenser and a dropping funnel.
85.5 g (1.0 mol) and 0.3 g (0.1 mmol) of tetrabutylphosphonium chloride were charged.

While maintaining the temperature at 40 ° C. and stirring vigorously, 250 ml of a 20% aqueous KOH solution was added dropwise over 1 hour. After the addition, the stirring was stopped and the lower organic layer was analyzed. 1,1,1, the raw material
2,2,3,3-heptachloropropane disappears and the organic layer is 1,
There was only 1,1,2,3,3-hexachloropropene.

The reaction solution was transferred to a separating funnel, and the organic layer was separated. After washing twice with saturated saline, drying over magnesium sulfate, 23
9 g (96%) of crude 1,1,1,2,3,3-hexachloropropene were obtained.

Example 13 1,1,1,2,2,3,3-heptachloropropane 2 was placed in a 500 ml round bottom flask equipped with a Dimroth condenser and a dropping funnel.
85.5 g (1.0 mol) and 0.3 g (0.1 mmol) of trioctylmethylammonium chloride were charged.

While maintaining the temperature at 40 ° C. and stirring vigorously, 250 ml of a 20% aqueous KOH solution was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was carried out for 2 hours. Thereafter, the stirring was stopped and the lower organic layer was analyzed. The raw material 1,1,1,2,2,3,3-heptachloropropane disappeared, and the organic layer was only 1,1,1,2,3,3-hexachloropropene.

The reaction solution was transferred to a separating funnel, and the organic layer was separated. After washing twice with saturated saline, drying over magnesium sulfate, 23
7 g (95%) of crude 1,1,1,2,3,3-hexachloropropene were obtained.

Comparative Example 1 1,1,1,2,2,3,3-heptachloropropane 2 was placed in a 500 ml round bottom flask equipped with a Dimroth condenser and a dropping funnel.
85.5 g (1.0 mol) was charged.

While maintaining the temperature at 40 ° C. and stirring vigorously, 250 ml of a 20% aqueous KOH solution was added dropwise over 1 hour. After the completion of the dropwise addition, the reaction was carried out for 3 hours. Thereafter, the stirring was stopped and the lower organic layer was analyzed.

The reaction has progressed only slightly and 63% of the organic layer is the raw material 1,1,1,2,2,3,3-heptachloropropane,
The conversion was 37%.

Example 14 The aqueous alkali solution used was changed from a 20% aqueous KOH solution to 20% NaOH
The reaction was carried out in the same manner as in Example 11 except that the solution was replaced with an aqueous solution. As a result, 232 g (93%) of crude 1,1,1,2,3,3-hexachloropropene was obtained.

Example 15 SbCl ₅ to 500ml Hastelloy autoclave equipped with a condenser 29.9 g (0.1 mol), and SbCl ₃ 22.9g (0.1mol)
The reaction was carried out in the same manner as in Example 7, except that it was added.

194 g of organic matter was obtained as a product. GLC confirmed that 98% of the product was the desired 1,1,1,3,3-pentafluoro-2,3-dichloropropane (93% yield). The main by-product was 1,1,1-tetrafluoro-2,3,3-trichloropropane, and no chlorine-added compound was found.

Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C07C 17/20 C07C 17/20 17/35 17/35 // C07B 61/00 300 C07B 61/00 300 (56) References JP2 −204443 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C07C 19/08 C07C 17/00 C07C 17/20 C07C 17/35

Claims (19)

(57) [Claims] 1. A method comprising reacting 1,1,1,3,3-pentafluoro-2,3-dichloropropane with hydrogen by a gas phase method in the presence of a noble metal catalyst to perform hydrogen reduction. 1,1,1,3,3-
A method for producing pentafluoropropane. 2. The method according to claim 1, wherein the noble metal catalyst is supported on a carrier comprising at least one selected from activated carbon, silica gel, titanium oxide and zirconia. 3. The concentration of a noble metal catalyst supported on a carrier is from 0.05 to 0.05.
3. The method according to claim 2, wherein the amount is 10%. 4. The production method according to claim 1, wherein the noble metal catalyst is made of palladium. 5. The method according to claim 1, wherein the hydrogenation is performed on 1,1,1,3,3-pentafluoro-2,3-dichloropropane using at least a stoichiometric amount of hydrogen. The manufacturing method according to any one of Items 4 to 4. 6. The production method according to claim 1, wherein the reaction is carried out in a temperature range of 30 to 450 ° C. 7. A method according to claim 1, wherein 1,1,1,3,3-pentafluoro-2,3-dichloropropane is prepared by adding at least one element selected from zirconium and vanadium to palladium. A method for producing 1,1,1,3,3-pentafluoropropane, comprising reacting with hydrogen by a gas phase method to reduce hydrogen. 8. A catalyst in which at least one element selected from zirconium and vanadium is added to palladium, the catalyst is supported on a carrier comprising at least one selected from activated carbon, silica gel, titanium oxide and zirconia. Item 8. The manufacturing method according to Item 7, wherein 9. The process according to claim 8, wherein the concentration of the catalyst on the carrier in which at least one element selected from zirconium and vanadium is added to palladium is 0.05 to 10%. Method. 10. The method according to claim 7, wherein the hydrogenation is performed on 1,1,1,3,3-pentafluoro-2,3-dichloropropane using at least a stoichiometric amount of hydrogen. 10. The production method according to any one of items 9 to 9. 11. The process according to claim 7, wherein the reaction is carried out in a temperature range of 30 to 450 ° C. 12. A compound of the general formula I: Is fluorinated in the liquid phase with hydrogen fluoride in the presence of antimony trihalide and / or antimony pentahalide. 9. The method according to claim 1, wherein 5 or more moles of hydrogen fluoride is present in the reaction system.
A method for producing 3,3-pentafluoro-2,3-dichloropropane. 13. While maintaining the reaction at a constant pressure, a starting material, propane halide and hydrogen fluoride are charged into the reaction system to produce 1,1,1,3,3-pentafluoro-2,3-diphenyl. 13. The production method according to claim 12, wherein chloropropane is extracted. 14. The production method according to claim 12, wherein the halogenated propene represented by the general formula I is 1,1,1,2,3,3-hexachloropropene. 15. The 1,1,1,1 obtained by reacting 1,1,1,2,2,3,3-heptachloropropane with an aqueous solution of an alkali metal hydroxide in the presence of a phase transfer catalyst. 2,1,3,3-Hexachloropropene is prepared by the method according to any one of claims 12 to 14, 1,1,1,3,3-pentafluoro-2,3-dichloropropane. Which is led to 1,1,1,3,3-pentafluoropropane by the production method according to any one of claims 1 to 11, A method for producing 3,3-pentafluoropropane. 16. The production method according to claim 15, wherein the phase transfer catalyst is a tetraalkylammonium salt. 17. The method according to claim 15, wherein the phase transfer catalyst is a tetraalkylphosphonium salt. 18. The 1,1,1,2,3,3- compound obtained by the method according to any one of claims 15 to 17 of the present invention.
Hexachloropropene was converted to 1,1,1,3,3-pentafluoro-
Claims 12 to 15 leading to 2,3-dichloropropane
Item 15. The method according to any one of items 14. 19. The 1,1,1,3,3-pentafluoro-2,3-dichloropropane obtained by the production method according to any one of claims 12 to 14 of the present invention. 1,1,1,3,3-pentafluoropropane is led to 1,1,1,1, by the production method according to any one of claims 1 to 11.
A method for producing 3,3-pentafluoropropane.